WO2011028934A1 - Fibers comprising at least one filler, processes for their production, and uses thereof - Google Patents
Fibers comprising at least one filler, processes for their production, and uses thereof Download PDFInfo
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- WO2011028934A1 WO2011028934A1 PCT/US2010/047722 US2010047722W WO2011028934A1 WO 2011028934 A1 WO2011028934 A1 WO 2011028934A1 US 2010047722 W US2010047722 W US 2010047722W WO 2011028934 A1 WO2011028934 A1 WO 2011028934A1
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- carpet
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- preferably less
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
Definitions
- the disclosure herein generally discusses and relates to fibers, particularly staple fibers comprising fillers such as coated ground calcium
- monofilament fibers may be used to make staple fibers, yarns, fishing line, woven fabrics, non-woven fabrics, artificial furs, diapers, feminine hygiene products, adult incontinence products, packaging materials, wipes, towels, industrial garments, medical drapes, medical gowns, foot covers, sterilization wraps, table cloths, surface cleaning cloths (dry and wet), paint brushes, napkins, trash bags, various personal care articles, and other textile products.
- Monofilament fibers are generally made by melt spinning, dry spinning, or wet spinning.
- monofilament fibers may be produced by spinning a polymeric resin into the shape of a fiber, for example, by heating the resin at least to its softening temperature and extruding the resin through a spinneret to form monofilament fibers.
- Monofilament fibers may also be produced by extruding the resin and attenuating the streams of resin by hot air to form fibers with a fine diameter.
- monofilament fibers, after conversion into staple fibers can be used to make spunlaced (also referred to as hydro-entangled), needle- punched, thermal bonded, and card-and-bind products, which can be disposed on a web.
- carpet may be made using yarn comprised of polypropylene, polyester, nylon, or a combination thereof, for example.
- the yarn may be formed from bulk continuous filament or staple fibers.
- staple fibers When staple fibers are used, the staple fibers may be carded to align the fibers parallel to each, thus forming large, soft, untwisted strands or ropes of fibers (i.e., slivers of fibers).
- the slivers may be combed and stretched using a pin-drafting machine, for instance. Then, a spinning machine may be used to stretch the sliver further and to twist the yarn to a desired size.
- Single strands of yarn are usually twisted with other strands of yarn to make a yarn suitable for making carpet.
- Processes for making carpet generally involve weaving or stitching.
- carpets are produced by stitching (i.e., tufting) using needles that punch yarn into a backing material (e.g., a pre-woven fabric) at regular intervals to form raised loops, or tufts.
- An adhesive may be applied to the back of the backing material to secure the tufts.
- the tufts may be cut, resulting in cup-pile carpet, or may be left uncut, resulting in looped-pile carpet.
- thermoplastic polymeric resin each year, about 300 million pounds of monofilament fiber. While it is known to incorporate various mineral fillers such as calcium carbonate and kaolin during production of non-woven products and plastic products such as films and molded parts, it is not currently the general practice to include large amounts of such fillers in monofilament fibers.
- mineral fillers such as calcium carbonate and kaolin
- the cost of virgin resin was lower than the cost of concentrates composed of resins and mineral fillers and, thus, no need existed for incorporating appreciable amounts of such fillers.
- increases in resin prices have created, in many instances, a cost benefit associated with increasing the quantity of mineral fillers and decreasing the quantity of resin in many products.
- the required amount of virgin resin material decreases while the end product may have comparable quality in areas including but not limited to fiber strength, texture, and appearance.
- Products comprising various amounts of inorganic compounds and/or mineral fillers have been known.
- U.S. Patent No. 6,797,377 appears to disclose non-woven webs comprising from 0.1 to 10 wt% of at least one mineral filler such as calcium carbonate, but imposes the limitation of the filler being used in conjunction with titanium dioxide in a mixture of at least two resin polymers.
- U.S. Patent No. 6,759,357 likewise appears to disclose fabrics comprising from 0.00 5 to 0.09 wt% of at least one inorganic compound. S. Nago and Y. Mizutani,
- Microporous Polypropylene Fibers Containing CaC0 3 Filler 62 J. Appl. Polymer Sci. 81-86 (1996), also appears to discuss polypropylene-based non-woven fibers comprising 25 wt% calcium carbonate.
- WO 97/30199 may disclose/fibers
- the present disclosure generally describes fibers, such as staple fibers, comprising at least one polymeric resin and at least one filler having an average particle size less than or equal to about 3 microns.
- the staple fibers comprise at least one polymeric resin, such as polypropylene, and at least one filler, such as surface-treated ground calcium carbonate (GCC).
- GCC surface-treated ground calcium carbonate
- Particular embodiments of the fibers can be converted into carded webs or used in carpet with little or no added rayon or titania to produce fibrous webs or carpet possessing physical properties equal to or better than similar fibers or carpet containing rayon.
- Certain embodiments of the webs can be formed into fabrics to produce various useful articles, such as baby wipes, surgical gowns, and surface cleaning cloths (wet or dry).
- the application discloses a process for producing staple fibers, the process comprises (a) mixing at least one polymeric resin with at least one coated ground calcium carbonate having an average particle size of less than or equal to about 3 microns; (b) heating the mixture to at least the softening point of the at least one polymeric resin; (c) extruding the mixture to form
- the present disclosure describes a carpet comprising a plurality of fibers including at least one polymeric resin and at least one coated filler, wherein the at least one coated filler has an average particle size of less than or equal to about 10 microns.
- Each of the fibers are adjoined to another of the fibers, a backing material, or both.
- Figure 1 is a graph showing the maximum force applied to each of the particular embodiments of the monofilament fiber before the fiber would break ("max load") for each percentage of stearic acid coated ground calcium carbonate in the fiber.
- Figure 2 is a graph showing the percent elongation of particular embodiments of the monofilament fibers for each percentage of stearic acid coated ground calcium carbonate in the fiber.
- Figure 3 is a graph showing the tenacity of particular embodiments of the monofilament fibers for each percentage of stearic acid coated ground calcium carbonate in the fiber.
- Figure 4 is a schematic diagram of an exemplary arrangement for making hydro-entangled multifilament webs of staple fibers.
- Figure 5 is a graph showing the stress-strain curves for particular embodiments of filled and unfilled multifilament fibers.
- Figure 6 is a graph showing the maximum machine direction force applied to various embodiments of filled and unfilled spunlaced fabrics before the fabrics would break ("max load").
- Figure 7 is a graph showing the maximum cross direction force applied to various embodiments of filled and unfilled spunlaced fabrics before the fabrics would break ("max load").
- Figure 8 is a graph showing the opacity for various embodiments of filled and unfilled spunlaced fabrics.
- Figures 9A and 9B are graphs showing the results of color testing on carpet made in accordance with embodiments of the present invention, as
- varying the particle size of at least one filler in polymeric fibers such as decreasing the particle size below about 0 microns (i.e., a top cut of less than or equal to 10 microns) and/or decreasing the average particle size to 3 microns or less, allows the polymeric fibers to retain or improve desirable properties (e.g., maximum loading, elongation at break, and/or tenacity) while increasing the overall quantity (measured as wt%) of filler in the fiber.
- fiber includes not only conventional single fibers and filaments (such as staple fibers and monofilament fibers), but also yarns made from a multiplicity of these fibers.
- yarns are utilized in the manufacture of apparel, fabrics, textiles (e.g., carpet) and the like.
- the characteristics disclosed herein for various embodiments of fibers serve as disclosures of the characteristics of certain embodiments of staple fibers and monofilament fibers, among other types of fibers.
- fibers and yarns may be made into fabrics using any methods currently used or hereafter discovered for making fibers and yarns into fabrics, including but not limited to weaving and knitting.
- staple fibers can also be made into non-woven webs and fabrics using any methods currently used or hereafter discovered, including spunlacing, needle-punching, thermal bonding, and card-and-bind processing.
- staple fibers refer to discrete fibers having a particular length.
- the staple fibers may have a length ranging from about 25 mm to about 50 mm.
- the staple fiber may have a length ranging from about 35 mm to about 100 mm.
- the staple fiber may have a length ranging from about 50 mm to about 75 mm.
- “monofilament fibers” refers to a single strand of material which may contain one large fiber or many smaller fibers intertwined together. In some embodiments, the monofilament fiber may be an untwisted fiber.
- the fiber including at least one polymeric resin and at least one coated filler has a first maximum load equal to or greater than a second maximum load of a second fiber including the at least one polymeric resin, but which is devoid of the at least one coated filler.
- the maximum load for a given fiber will depend upon composition, size, and process variables such as percent draw.
- the fiber has a maximum load ranging from about 2 Ibf to about 20 Ibf.
- the fiber has a maximum load ranging from about 5 Ibf to about 15 Ibf.
- the fiber has a maximum load ranging from about 7 Ibf to about 10 Ibf.
- the fiber including at least one polymeric resin and at least one coated filler has a first elongation at break equal to or greater than a second elongation break of a second fiber including the at least one polymeric resin, but which is devoid of the at least one coated filler.
- the elongation to break depends primarily on the amount of draw during production. Comparing elongation to break results on fibers produced using the same process conditions illustrates the values decrease only slightly with the addition of filler.
- the fiber containing 10 percent calcium carbonate has a decrease in elongation at break ranging from about 0% to about 50%.
- the fiber has a decrease in elongation at break ranging from about 0% to about 25%.
- the fiber has a decrease in elongation at break ranging from about 0% to about 10%.
- the fiber including at least one polymeric resin and at least one coated filler has a first tenacity equal to or greater than a second tenacity of a second fiber including the at least one polymeric resin, but which is devoid of the at least one coated filler.
- Tenacity indicates the load to break a fiber or fibers normalized for the fiber diameters.
- the tenacity for a given fiber can depend upon composition, size, and process variables such as percent draw. For example, in the case of 2 denier polypropylene fibers, the fiber can have a first tenacity ranging from about 2 grams/denier to about 10 grams/denier.
- the fiber can have a first tenacity ranging from about 3 grams/denier to about 8 grams/denier. In still other embodiments, the fiber has a first tenacity ranging from about 4 grams/denier to about 7 grams/denier.
- the fibers disclosed herein comprise at least one polymeric resin.
- the at least one polymeric resin is chosen from conventional polymeric resins that provide the properties desired for any particular staple fiber, yarn, woven product, non-woven product, or application.
- the at least one polymeric resin is chosen from thermoplastic polymers, including but not limited to: polyolefins, such as polypropylene and polyethylene homopolymers and copolymers, including copolymers with 1-butene, 4-methyl-1-pentene, and 1-hexane; polyamides, such as nylon; polyesters; and copolymers of any of the above-mentioned polymers.
- the monofilament fibers consist essentially of a polymeric resin, such as polypropylene, and a filler, such as coated GCC.
- the at least one polymeric resin is an isotropic semi-crystalline polymer.
- the isotropic semi-crystalline polymer is melt-processable, melting in a temperature range that makes it possible to spin the polymer into fibers in the melt phase without significant decomposition.
- Exemplary isotropic semi-crystalline polymers include, but are not limited to, poly(alkylene terephthalates); poly(alkylene naphthalates); poly(arylene sulfides); aliphatic and aliphatic-aromatic polyamides; polyesters comprising monomer units derived from cyclohexanedimethanol and terephthalic acid; poly( ethylene terephthalate); poly(butylene terephthalate); poly( ethylene naphthalate);
- the at least one polymeric resin is a semi-crystalline polymer polyolefin, including but not limited to polyethylene and polypropylene.
- the at least one polymeric resin is an extended chain polyethylene having a high tensile modulus, made by the gel spinning or the melt spinning of very or ultrahigh molecular weight polyethylene.
- Isotropic polymers that may not be processable in a melt may also be used as the at least one polymeric resin in embodiments of the present inventions.
- the isotropic polymer is rayon.
- the isotropic polymer is cellulose acetate.
- the isotropic polymer is polybenzimidazole, poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole].
- the isotropic polymers are dry spun using acetone as a solvent.
- poly [2,2'-(m-phenylene)-5,5'-bibenzimidazole] is wet spun using ⁇ , ⁇ '-dimethylacetamide as a solvent.
- the isotropic polymers are aromatic polyamides other than the polymer of terephthalic acid and p-phenylene diamine (e.g., polymers of terephthalic acid and one or more aromatic diamines) that are soluble in polar aprotic solvents, including but not limited to N-methylpyrrolidinone, that are wet spun with added particles to yield fibers such as monofilament fibers.
- amorphous, noncrystalline, isotropic polymers including but not limited to the copolymer of isophthalic acid, terephthalic acid and bisphenol A (polyarylate), may also be filled (i.e., include a filler) and utilized in the present inventions.
- the at least one polymeric resin is made from a liquid crystalline polymer (LCP).
- LCPs produce fibers with high tensile strength and/or modulus.
- the liquid crystalline polymer is processable in a melt (i.e., thermotropic).
- the liquid crystalline polymer cannot be processed in a melt.
- liquid crystalline polymers are used that exhibit liquid crystalline behavior in solution, are blended with a hard filler, and then wet or dry spun to yield monofilament fibers.
- the aromatic polyamide made from p- phenylenediamine and terephthalic acid can be filled and wet spun (e.g., by dry-jet wet- spinning from a concentrated sulfuric acid solution) to yield fibers such as
- the liquid crystalline polymer is any aromatic polyamide that is soluble in polar aprotic solvents, including but not limited to N-methylpyrrolidinone, and that can be spun into monofilament fibers or staple fibers.
- the liquid crystalline polymer is not liquid crystalline under some or all of a given condition or set of conditions, but still yields high modulus fibers.
- the liquid crystalline polymer exhibits lyotropic liquid crystalline phases at some concentrations and in some solvents, but isotropic solutions at other concentrations and/or in other solvents.
- the liquid crystalline polymers (LCPs) for use in this invention are thermotropic LCPs.
- Exemplary thermotropic LCPs include, but are not limited to, aromatic polyesters, aliphatic-aromatic polyesters, aromatic poly(esteramides), aliphatic-aromatic poly(esteramides), aromatic poly(esterimides), aromatic poly(estercarbonates), aromatic polyamides, aliphatic-aromatic
- thermotropic LCPs are aromatic polyesters and poly(esteramides) that form liquid crystalline melt phases at temperatures less than about 360 °C and include one or more monomer units derived from the group consisting of terephthalic acid, isophthalic acid, 1 ,4- hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-biphenyldicarboxylic acid, 4- hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 4-aminophenol, and 4-aminobenzoic acid.
- the aromatic groups include substituents which do not react under the conditions of the polymerization, such as lower alkyl groups having 1-4 carbons, aromatic groups, F, CI, Br, and I.
- substituents which do not react under the conditions of the polymerization such as lower alkyl groups having 1-4 carbons, aromatic groups, F, CI, Br, and I.
- the synthesis and structure of some typical aromatic polyesters are taught in U.S. Pat. Nos. 4,473,682; 4,522,974; 4,375,530; 4,318,841; 4,256,624; 4,161 ,470; 4,219,461 ; 4,083,829; 4,184,996; 4,279,803;
- the LCPs have monomer repeat units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, as taught in U.S. Pat. No. 4,161 ,470.
- the monomer units derived from 4- hydroxybenzoic acid comprise about 15% to about 85% of the polymer on a mole basis
- monomer units derived from 6-hydroxy-2-naphthoic acid comprise about 85% to about 15% of the polymer on a mole basis.
- the polymer comprises about 73% monomer units derived from 4-hydroxybenzoic acid and about 27% monomer units derived from 6-hydroxy-2-naphthoic acid, on a mole basis.
- Such a polymer is available in fiber form under the VECTRAN trademark from Hoechst Celanese Corporation, Charlotte, N.C.
- the LCPs or poly(esteramides) comprise the above recited monomer units derived from 6-hydroxy-2-naphthoic acid and 4- hydroxybenzoic acid, as well as monomer units derived from one or more of the following monomers: 4,4'-dihydroxybiphenyl, terephthalic acid, and 4-aminophenol.
- the polyester comprising these monomer units is derived from 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-biphenol, and terephthalic acid, as taught in U.S. Pat. No.
- the poly(esteramide) comprises monomer units derived from 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, terephthalic acid, 4,4'-biphenol, and 4-aminophenol, as taught in U.S. Pat. No. 5,204,443.
- the composition comprises these monomer units in a mole ratio of about 60:3.5: 8.25:13.25:5.
- the at least one polymeric resin is a suitable commercial polymeric resin product.
- Exemplary commercial products suitable as the at least one polymeric resin include, but are not limited to: Basell Pro-fax 6323 polypropylene resin, a general purpose homopolymer with a density of about 0.9 g/cm 3 and a melt flow index of about 12.0 g/10 min, available from LyondellBasell Industries; Exxon 3 55, a polypropylene homopolymer having a melt flow rate of about 30 g/10 min, available from Exxon Mobil Corporation; PF 305, a
- the at least one polymeric resin may be present in the monofilament fibers of the present disclosure in an amount of greater than or equal to about 50 wt%, relative to the total weight of the fibers. In one embodiment, the at least one polymeric resin is present in the fibers in an amount ranging from about 50 to about 90 wt%. In another embodiment, the at least one polymeric resin is present in the fibers in an amount ranging from about 75 to about 90 wt%.
- the fibers comprise at least one filler.
- the at least one filler is any mineral-based substrate capable of being coated, mixed with at least one polymeric resin, and extruded.
- the at least one filler is coated ground calcium carbonate. Coated ground calcium carbonate is a filler commonly used in the formation of various polymeric products.
- the at least one filler is chosen from the group consisting of coated ground calcium carbonate, limestone, talc, and clay products.
- the at least one filler is a clay product chosen from the group consisting of kaolins and calcined clays.
- Exemplary coated ground calcium carbonate products suitable for use as an at least one filler include, but are not limited to, those commercially available.
- the coated ground calcium carbonate is chosen from those products sold under the name FiberLinkTM by Imerys, Inc.
- the coated ground calcium carbonate is the product sold under the name MAGNUM GLOSS ® by the Mississippi Lime Company.
- the coated ground calcium carbonate is the product sold under the name ALBAGLOS ® by Specialty Minerals, Inc.
- the coated ground calcium carbonate is the product sold under the name OMYACARB ® by OMYA, Inc.
- the coated ground calcium carbonate is the product sold under the name HUBERCARB ® by Huber, Inc. In still another embodiment, the coated ground calcium carbonate is the product sold under the name FiberLinkTM 101S by Imerys, Inc. Exemplary commercially available coated ground calcium carbonate products may be available in the form of dry powders having defined particle size ranges; however, not all commercial coated ground calcium carbonate products will exhibit a particle size and distribution appropriate for use in
- the particle size of the at least one filler may affect, among other things, the maximum amount of filler effectively
- the at least one filler may be used to provide preferred physical properties to fibers, for example, by increasing the strength and/or imparting desirable roughness and/or opacity to staple fibers. Such characteristics may be desirable in various
- hygienic products e.g., baby wipes
- surgical gowns e.g., surgical gowns
- cleansing products e.g., surface cleaning cloths (wet and dry)
- the at least one filler has an average particle size less than or equal to about 10 microns. In another embodiment, the at least one filler has an average particle size ranging from about 1 micron to about 10 microns. In a further embodiment, the at least one filler has an average particle size of about 1 micron. In yet another embodiment, the at least one filler has an average particle size less than or equal to about 4 microns. In yet a further embodiment, the at least one filler has an average particle size less than or equal to about 3 microns. In still another embodiment, the at least one filler has an average particle size less than or equal to about 2 microns. In still a further embodiment, the at least one filler has an average particle size less than or equal to about 1.5 microns. In another
- the at least one filler has an average particle size less than or equal to about 1 micron. In a further embodiment, the at least one filler has an average particle size ranging from about 1 micron to about 4 microns. In yet another embodiment, the at least one filler has an average particle size ranging from about 1 micron to about 3 microns. In yet a further embodiment, the at least one filler has an average particle size ranging from about 1 micron to about 2 microns. In still another embodiment, the at least one filler has an average particle size ranging from about 0.5 microns to about 1.5 microns. Average particle size is defined herein as the d 5 o as measured on a Microtrac ® 100 particle size analyzer.
- the at least one filler may be characterized by a "top cut” value.
- top cut refers to the largest particle size that can be identified in a sample of filler by a Microtrac® 100 particle size analyzer.
- the top cut is less than about 10 microns.
- the top cut is less than about 8 microns.
- the top cut is less than about 6 microns.
- the top cut is less than about 4 microns.
- the top cut ranges from about 4 microns to about 10 microns.
- the top cut ranges from about 4 microns to about 8 microns.
- the top cut ranges from about 4 microns to about 6 microns.
- the top cut is less than the diameter of the fibers.
- the at least one filler has a top cut less than or equal to about 65%, more preferably less than or equal to about 70%, and most preferably less than or equal to about 75%, of the fiber diameter.
- the at least one filler has a top cut less than or equal to about 60% of the fiber diameter.
- the particle size distribution of the at least one filler according to the present disclosure may be small enough so as to not significantly weaken the individual fibers and/or make the surface of the fibers abrasive, but large enough so as to create an aesthetically pleasing surface texture.
- the particle size distribution of the at least one filler has less than about 5% of the total particles greater than about 10 microns, and less than about 5% of the total particles less than about 0.5 microns.
- particles above about 10 microns may tend to weaken the structure, and particles less than about 0.5 microns may tend to form agglomerates, leading to formation of structures greater than about 10 microns.
- the at least one filler may be coated with at least one organic material.
- the at least one organic material is chosen from fatty acids, including but not limited to stearic acid, and salts and esters thereof, such as stearate.
- the at least one organic material is ammonium stearate.
- the at least one organic material is calcium stearate.
- the products sold under the tradename FiberLinkTM by Imerys, Inc. are non-limiting examples of ground calcium carbonate products coated with stearic acid.
- Surface coating the at least one filler with at least one organic material may, in some embodiments, serve to improve dispersion of the at least one filler particles throughout the fiber and/or facilitate the overall production of the fibers.
- uncoated ground calcium carbonate to at least one polymeric resin, as opposed to coated ground calcium carbonate, results in fibers having uncoated ground calcium carbonate particles located on the outside of the fibers, which may be problematic because uncoated particles located on the outside of the fibers may cause inorganic deposits to attach to metal components of the spinneret die holes and clog the exit holes, thus preventing the fibers from extruding properly.
- the amount of the at least one filler may negatively impact the strength and/or surface texture of the monofilaments fibers if it exceeds a certain value.
- the at least one filler is present in an amount less than about 50 wt%, relative to the total weight of the fibers.
- the at least one filler is present in an amount less than about 25 wt%.
- the at least one filler is present in an amount less than about 20 wt%.
- the at least one filler is present in an amount less than about 15 wt%.
- the at least one filler is present in an amount less than about 10 wt%.
- yet still another another filler is present in an amount less than about 50 wt%, relative to the total weight of the fibers.
- the at least one filler is present in an amount less than about 25 wt%.
- the at least one filler is present in an amount less than about 20 wt%.
- the at least one filler is present in an amount less than about 15 wt%
- the at least one filler is present in an amount ranging from about 5 wt% to about 40 wt%. In still another embodiment, the at least one filler is present in an amount ranging from about 10 wt% to about 20 wt%. In still another embodiment, the at least one filler is present in an amount ranging from about 10 wt% to about 15 wt%. In yet another embodiment, the at least one filler is present in an amount from about 10 wt% to about 25 wt% when the at least one filler has an average particle size of less than about 3 microns and/or a top cut of less than about 10 microns.
- embodiments of the fibers may further comprise at least one additive.
- the at least one additive may be chosen from those now known in the art or those hereafter discovered.
- the at least one additive is chosen from additional mineral fillers, including but not limited to, talc, gypsum, diatomaceous earth, kaolin, attapulgite, bentonite, montmorillonite, and other natural or synthetic clays.
- the at least one additive is chosen from inorganic compounds, including but not limited to silica, alumina, magnesium oxide, zinc oxide, calcium oxide, and barium sulfate.
- the at least one additive is chosen from one of the group consisting of: optical brighteners; heat stabilizers; antioxidants; antistatic agents; anti-blocking agents; dyestuffs; pigments, including but not limited to titanium dioxide; luster improving agents; surfactants; natural oils; and synthetic oils.
- fibers as discussed herein, may be
- melt spinning which may employ an extrusion process to provide molten polymer mixtures to spinneret dies.
- melt spinning may be accomplished using DuPont fiber spinning equipment, such as that available at the time this application was filed at Clemson University in Clemson, South Carolina, USA.
- the process for producing fibers according to the present invention comprises heating the at least one polymeric resin to at least about its softening point. In another embodiment, the process comprises heating the at least one polymeric resin to any temperature suitable for the extrusion of the at least one polymeric resin. In a further embodiment, the at least one polymeric resin is heated to a temperature ranging from about 225 °C to about 260 °C.
- the at least one filler may be incorporated into the at least one polymeric resin using any method conventionally known in the art or hereafter discovered.
- the at least one filler may be added to the at least one polymeric resin during any step prior to extrusion, for example, during or prior to the heating step.
- a "masterbatch" of at least one polymeric resin and the at least one filler may be premixed, optionally formed into granulates or pellets, and mixed with at least one additional virgin polymeric resin before extrusion of the fibers.
- masterbatch refers to mixture, dispersion, or suspension of components, such as a filler, and a polymeric resin.
- the at least one additional virgin polymeric resin may be the same or different from the at least one polymeric resin used to make the masterbatch.
- the masterbatch comprises a higher concentration of the at least one filler, for instance, a concentration ranging from about 20 wt% to about 75 wt%, than is desired in the fiber, and may be mixed with the at least one additional polymeric resin in an amount suitable to obtain the desired concentration of at least one filler in the fiber.
- the concentration of the at least one filler in the masterbatch is about 20 wt% to about 75 wt%.
- the concentration of the at least one filler in the masterbatch is about 20 wt% to about 50 wt%.
- a masterbatch comprising 50 wt% coated ground calcium carbonate may be mixed with an equal amount of at least one virgin polymeric resin to produce a final product comprising 25 wt% coated ground calcium carbonate.
- the masterbatch may be mixed and pelletized using any apparatus known in the art or hereafter discovered, for example, a ZSK 30 Twin Extruder may be used to mix and extrude the coated ground calcium carbonate and at least one polymer resin masterbatch, and a Cumberland pelletizer may be used to optionally form the masterbatch into pellets.
- the mixture may be extruded continuously through at least one spinneret to produce long filaments.
- the extrusion rate may vary according to the desired application, and appropriate extrusion rates will be known to the skilled artisan.
- the extrusion temperature may also vary depending on the desired application and process. In one embodiment, the extrusion temperature ranges from about 225 °C to about 260 °C. In another embodiment, the extrusion temperature ranges from about 235 °C to about 245 °C. In certain embodiments, the extrusion apparatus may be chosen from those conventionally used now or hereafter discovered in the art. In one embodiment, the extrusion apparatus is an Alex James 0.75 inch single screw extruder with a 0.297 cc/rev metering pump. In some embodiments, the at least one spinneret may be chosen from those conventionally used now or hereafter discovered in the art. In one embodiment, the at least one spinneret contains 10 holes, each about 0.022 inches in diameter.
- the fibers may be attenuated.
- the fibers are attenuated by high-speed drawing, in which the multi-strand filament is drawn out on rollers such that the wind speed is about 1000 meters per minute.
- monofilament fibers may be made by melt spinning, dry spinning, or wet spinning.
- monofilament fibers may be produced by spinning a polymeric resin into the shape of a fiber by heating the resin at least to its softening temperature and extruding the resin through a spinneret to form monofilament fibers.
- monofilament fibers may also be produced by extruding the resin and attenuating the streams of resin by hot air to form fibers with a fine diameter.
- a method for producing monofilament fibers comprises adding at least one filler to at least one polymeric resin and extruding the resulting mixture, wherein the at least one filler is present in the final product in an amount of less than or equal to about 50% by weight.
- monofilament fibers may be produced according to any appropriate process or processes now known to the skilled artisan or hereafter discovered, that result in the production of a continuous monofilament fiber comprising at least one polymeric resin and at least one filler.
- the fibers may be produced to have a desired size.
- the fibers range in size from about 0.1 denier to about 120 denier.
- the fibers range in size from about 1 denier to about 100 denier.
- the fibers range in size from about 0.5 to about 5 denier.
- the fibers are about 100 denier in size
- monofilament fibers can be processed further using conventional techniques and equipment used in the textile art, to produce staple fibers.
- the monofilament fibers in extruded continuous form, can be subjected to a steamer unit for preheating. Then, in certain embodiments, the continuous monofilament fibers can have a carding finish applied, followed by a crimping step to improve their processability.
- a cutting device can be used to deliver staple fibers having either uniform, substantially uniform, or varying lengths.
- multifilament webs can be made by, for example, introducing staple fibers to a first fiber opener, emptying them into a second fiber opener, and then sending the fibers over to cards.
- the carded web may be flowed onto a carding conveyor belt that leads to a crosslapper.
- the crosslapper disposes many layers of thin carded webs onto a needle-punch conveyor belt moving orthogonal or perpendicular to the carding conveyor.
- the basis weight of this stack of webs can be controlled by adjusting the relative speeds of the two belts.
- one or more needle-punching heads along the line can act to bond the webs, giving them integrity for further handling and processing.
- the webs can be bonded to a lesser degree, if desired, by passing them through a pre- entangler.
- the extent of needle-punching or pre-entangling can be adjusted to produce webs having particular basis weights.
- the webs can be run through a hydro-entangling process.
- a horizontal moving wire conveyor belt carries the webs under one or more vertical water spray heads 1 , 2, 3.
- One or more vacuum stations 4 underneath the belt remove the water, causing the fibers to become entangled.
- the process additionally can include equipment along the line adapted for providing improved bonding of the fibers and delivering a substantially uniform appearance on both sides of the webs.
- this improved bonding can be achieved through a method referred to as "back side entangling," where the webs are passed over a porous roll 5 that applies a vacuum while water spray heads 6, 7 spray the back side of the webs, before they pass into a drying oven and rewinder.
- back side entangling where the webs are passed over a porous roll 5 that applies a vacuum while water spray heads 6, 7 spray the back side of the webs, before they pass into a drying oven and rewinder.
- the addition of chemical binders advantageously may be avoided, and the fibers do
- carpet comprising a plurality of fibers including at least one coated filler and a polymeric resin are provided.
- the plurality of fibers may comprise the fibers described herein.
- the fibers or yarns of the carpet may include staple fibers.
- addition of a filler to the carpet fibers as disclosed herein reduces the amount of resin required to produce the carpet while still maintaining the wear and strength properties of the carpet fibers, which can provide advantageous economic benefits.
- other properties, such as gloss and/or electrostatic propensity desirably may be improved as compared to carpets comprising polymeric resin fibers that do not include coated fillers.
- the carpet may comprise woven or stitched fibers or yarn.
- the carpet may comprise yarns woven together such that each of the yarns are adjoined to at least another of the yarns.
- the carpet may include twisted yarn.
- the carpet may be cut pile carpet or uncut pile carpet.
- the carpet comprises yarn having a size ranging from 5 denier to about 50 denier. In other embodiments, the carpet comprises yarn having a size ranging from 10 denier to about 40 denier. In still other embodiments, the carpet comprises yarn having a size ranging from 15 denier to about 30 denier. [0064] In particular embodiments, the carpet may be stitched into a backing material or backing fabric. Suitable backing materials for use in embodiments of the carpet include, but are not limited to, woven polypropylene slit film and nonwoven polyester fabric.
- the carpet may include additive materials, such as synthetic SBR latex foam and polyvinyl chloride.
- the carpet has a 60 degree gloss ranging from about 0 to about 10. In other embodiments, the carpet has a 60 degree gloss ranging from about 0 to about 5. In still other embodiments, the carpet has a 60 degree gloss ranging from about 0 to about 2.5.
- the carpet has an electrostatic propensity ranging from about 0 kV to about 3 kV. In other embodiments, the carpet has an electrostatic propensity ranging from about 0 kV to about 0.5 kV. In still other embodiments, the carpet has an electrostatic propensity ranging from about 0 kV to about 0.1 kV.
- the carpet has a turf bind ranging from about 0 lbs to about 2 lbs. In other embodiments, the carpet has a turf bind ranging from about 4 lbs to about 10 lbs. In still other embodiments, the carpet has a turf bind ranging from about 6 lbs to about 8 lbs.
- the carpet has a first opacity equal to or greater than a second opacity of a second carpet comprising a plurality of second fibers including the at least one polymeric resin, but which is devoid of the at least one coated filler.
- the carpet has a first whiteness equal to or greater than a second whiteness of a second carpet comprising a plurality of second fibers including a comparable at least one polymeric resin, but which is devoid of the at least one coated filler.
- the carpet has a first brightness equal to or greater than a second brightness of a second carpet comprising a plurality of second fibers including a comparable at least one polymeric resin, but which is devoid of the at least one coated filler.
- the carpet has a first yellowness equal to or less than a second yellowness of a second carpet comprising a plurality of second fibers including a comparable at least one polymeric resin, but which is devoid of the at least one coated filler.
- a process for making carpet comprises providing a plurality of fibers comprising at least one polymeric resin and at least one coated filler, affixing each of the fibers to at least another of the fibers, to a backing material, or both.
- the plurality of fibers may comprise the fibers described herein.
- the carpet may be produced according to any appropriate process or processes now known to the skilled artisan or hereafter discovered. Exemplary processes include tufting, weaving, knitting, and needlepunching. For instance, tufting yarn with a tufting machine first involves threading hundreds of needles with yarn, the needles being positioned in a line across the face of the machine.
- each needle inserts the yarn into a primary backing fabric such that, below the needles, loopers catch the yarn and form individual loops.
- the yarn is entangled in the backing fabric so that it stays in place.
- the process for producing carpet may start with continuous yarn or with discrete staple fibers formed into yarns.
- the fibers disclosed herein may be tested by any number of various methods and for any number of various properties, including for their individual fiber strength, elongation at break, and tenacity. Those three tests may be conducted using, for example, ASTM D3822.
- the carpet disclosed herein may be tested by any number of various methods and for any number of various properties, including electrostatic
- Electrostatic propensity indicates the likelihood someone will pick up a static charge while walking across the carpet wearing shoes with rubber or leather soles. Electrostatic propensity may be measured using AATCC 134 - 1996.
- Pill flammability To measure pill flammability, a carpet sample is dried in an oven and then a flammable pill or tablet is placed in the center of the sheet and allowed to burn for 2 minutes. A passing grade means the flame did not speard more than 3 inches in any direction. Pill flammability may be measured using ASTM D2859-06.
- Turf bind test measures the force necessary to pull the carpet fibers out of the backing. Turf bind may be measured using ASTM D1335.
- Abrasion resistance may be measured using ASTM D3884 (Abrasion Wheels -H-18 with 1000 grams load).
- Color testing may be performed using the method of ASTM D2244.
- the at least one filler in this example was a low solids processed, uncoated ground calcium carbonate (Supermite ® , Imerys, Inc.) with an average particle size of about 1.5 microns and a top cut of about 10 microns.
- the filler was compounded at various weight percentages with Basell Profax 6323 polypropylene resin, a general purpose homopolymer with a density of 0.9 g/cm 3 and a melt flow index of 12.0 g/10 min. Monofilament fibers were produced, when possible, using a standard melt fiber spinning process. At 5% loadings, the uncoated product experienced immediate processing problems where even 4 denier fibers could not be produced, even at low line speeds, without fiber breaks. This trial was not conducted long enough for the powder to plate out and clog the spinneret holes, but previous evaluations indicate it would have happened.
- This example used as the at least one filler a low solids processed, stearic acid coated calcium carbonate with an average particle size of 1.5 micron and a top cut of 8 microns, sold by Imerys, Inc. under the trade name FiberLinkTM 101S.
- the stearic acid target was about 1 % by weight.
- the virgin resin was a 12 MFI homopolymer polypropylene supplied by Atofina.
- Fibers were extruded using a 10 hole die, which means that there were actually 0 fibers intertwined together. Tests of the resulting fibers were conducted using ASTM D3822y conditions at additive loadings of about 0%, about 5%, about 10%, about 20%, and about 50%. Continuous fibers were produced at target sizes of 4, 3, and 2 denier, using the same standard melt fiber spinning process as in Example 1. Prototypes containing about 50% additive loadings could not be produced at 2 denier. The strength properties of 3 denier monofilament fibers are shown in Figures 1 , 2, and 3 and summarized below in Table 1.
- the material produced in this example was polypropylene staple fibers, filled and unfilled, made into carded webs with and without rayon fibers.
- the target size was the same for each fiber type.
- the polypropylene fibers were formed on a fiber spinning line. The same spinning finish was applied to all of the fibers produced.
- the unfilled fibers were produced using 100% PP resin with a target denier of 1.5 and a cut length of 34 mm.
- the filled fibers were produced using 71.4% virgin PP resin blended with 28.6% Marx 09-006, a Washington Penn product consisting of 70% FiberLinkTM 101S (Imerys, Inc.) and 30% Exxon 3145 PP resin, yielding finished fibers containing 80% PP and 20% calcium carbonate.
- the rayon fibers, obtained from National Spinning, had a target denier of 1.2 and a staple length of .5 inches.
- the unfilled PP staple fiber webs were made by introducing 25 pounds of unfilled PP staple fibers to the first fiber opener, which in turn emptied into a second opener, before sending the fibers to the cards.
- the carded web flowed onto a conveyor belt and was directed to crosslapper.
- the web passed through a pre-entangler to keep the web sufficiently bound to be wound onto a core for running through the hydro-entangler. This web was adjusted to yield a 55 gsm basis weight at the conveyor belt at the position after the second needle punch station, and was passed through the hydro-entangler.
- Figure 5 shows that at the intended range of use for a nonwoven fabric - namely, under 100% elongation - the strength of the 20% filled fibers is uniformly superior to the unfilled fibers.
- FIG. 8 Another potentially desirable feature of nonwoven fabrics is opacity, which provides the end product with, for example, a whiter appearance.
- Figure 8 shows that the fabrics containing calcium carbonate are less transparent than unfilled fabrics, which may be desirable in some applications.
- the texture of a nonwoven fabric may be a desirable quality.
- softness is a desirable surface feel for baby wipes.
- the fabric of the present invention may surprisingly deliver a desirable, soft feel, for example, without compromising the strength of the material.
- Example 3 To simulate a popular consumer product, wet wipes, and draw meaningful comparisons, the tests were conducted with wet and dry fabrics.
- the wet fabrics were prepared by soaking the fabrics in a solution of 85% water, 10% aloe vera, and 5% ethyl alcohol. The sheets were suspended in air to drain excess liquid before being used.
- Each test constituted a comparison of two fabrics, with the subjects rating their preferences on a score sheet.
- Roswell test performed in Roswell, Georgia, U.S.A.
- each subject rated the two fabrics based on three directional qualities - softer, stronger, thicker - and identified which of the two compared fabrics was better overall.
- the results of the Roswell test are shown below in Tables 2, 3, and 4.
- the other test performed in Par Moor, England, the subjects were asked to rate one quality, softness.
- the results of the Par Moor test are shown below in Table 5.
- the first comparison involved fabrics made from standard polypropylene fibers, one without rayon fibers, and one with rayon fibers, akin to a commercial product.
- Commercial manufacturers conventionally add rayon fibers to PP to improve aesthetic and textural qualities of fabrics.
- the panel study results show that the fabric containing rayon fibers generally was preferred for the measured qualities, particularly when the fabrics were wet.
- the second comparison shows that the fabric containing rayon fibers generally was preferred for the measured qualities, particularly when the fabrics were wet.
- the lower number of cycles needed to abrade the carpet including the coated calcium carbonate may indicate that those yarns are softer. However, a value of 4500 may be used for indoor or outdoor carpet.
- FIGS 9A and 9B The color test properties of the carpet are shown in Figures 9A and 9B.
- Figure 9A the color properties of the filled samples are all better, with high values, that the control samples.
- Figure 9B for the filled samples are better, with lower values, in comparison to the control samples. In other words, more white and opaque are positive qualities while less yellow is a desirable property.
Landscapes
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
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Priority Applications (3)
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EP10814514.5A EP2473656B1 (en) | 2009-09-04 | 2010-09-02 | Carpet |
CN201080049758.4A CN102575386B (zh) | 2009-09-04 | 2010-09-02 | 一种地毯 |
EP15167394.4A EP2977492B1 (en) | 2009-09-04 | 2010-09-02 | Carded web |
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US12/554,371 | 2009-09-04 | ||
US12/554,371 US20100035045A1 (en) | 2008-01-21 | 2009-09-04 | Fibers comprising at least one filler and processes for their production |
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WO2011028934A1 true WO2011028934A1 (en) | 2011-03-10 |
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US (1) | US20100035045A1 (zh) |
EP (2) | EP2977492B1 (zh) |
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WO (1) | WO2011028934A1 (zh) |
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- 2010-09-02 EP EP15167394.4A patent/EP2977492B1/en not_active Revoked
- 2010-09-02 EP EP10814514.5A patent/EP2473656B1/en not_active Revoked
- 2010-09-02 TR TR2019/00653T patent/TR201900653T4/tr unknown
- 2010-09-02 CN CN201510716004.4A patent/CN105369381A/zh active Pending
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EP2473656B1 (en) | 2009-09-04 | 2015-05-13 | Imerys Pigments, Inc. | Carpet |
WO2012141977A1 (en) * | 2011-04-12 | 2012-10-18 | J.M. Huber Corporation | Narrow particle size distribution calcium carbonate and methods of making same |
US8987363B2 (en) | 2011-04-12 | 2015-03-24 | J.M. Huber Corporation | Narrow particle size distribution calcium carbonate and methods of making same |
US9193602B2 (en) | 2011-04-12 | 2015-11-24 | Huber Carbonates, Llc | Narrow particle size distribution calcium carbonate and methods of making same |
EP2963162A1 (en) | 2014-07-01 | 2016-01-06 | Omya International AG | Multifilament polyester fibres |
US11208738B2 (en) | 2014-07-01 | 2021-12-28 | Omya International Ag | Multifilament polyester fibres |
EP2975078A1 (en) | 2014-08-14 | 2016-01-20 | Omya International AG | Surface-treated fillers for breathable films |
US10287407B2 (en) | 2014-08-14 | 2019-05-14 | Omya International Ag | Surface-treated fillers for breathable films |
EP3176204A1 (en) | 2015-12-02 | 2017-06-07 | Omya International AG | Surface-treated fillers for ultrathin breathable films |
US10941279B2 (en) | 2015-12-02 | 2021-03-09 | Omya International Ag | Surface-treated fillers for ultrathin breathable films |
WO2021005182A1 (en) | 2019-07-11 | 2021-01-14 | Omya International Ag | Nonwoven fabric and process for the production thereof |
US12060666B2 (en) | 2019-07-11 | 2024-08-13 | Omya International Ag | Nonwoven fabric and process for the production thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102575386A (zh) | 2012-07-11 |
EP2473656B1 (en) | 2015-05-13 |
EP2977492B1 (en) | 2018-11-07 |
CN105369381A (zh) | 2016-03-02 |
EP2473656A1 (en) | 2012-07-11 |
EP2977492A1 (en) | 2016-01-27 |
US20100035045A1 (en) | 2010-02-11 |
TR201900653T4 (tr) | 2019-02-21 |
EP2473656A4 (en) | 2013-05-01 |
CN102575386B (zh) | 2015-12-02 |
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